Indirect coupling

An example of a direct spectrophotometrical assay is the use of synthetic peptide -nitroanilide substrates to determine protease activity. The /)-nitroani1ine group Hberated from the substrates by the protease can be determined spectrophotometricaHy at 410 nm. An example of an indirect (coupled) spectrophotometric assay is the determination of a-amylase using -nitrophenyLmaltoheptaoside. Initially, the substrate is cleaved by the a-amylase and subsequentiy one of the reaction products, -nitrophenyLmaltotrioside, is cleaved by a-glucosidase, hberating -nitrophenyl, a chromophore... 

An excellent example of PLC applications in the indirect coupling version is provided by the works of Miwa et al. [12]. These researchers separated eight phospholipid standards and platelet phospholipids from the other lipids on a silica gel plate. The mobile phase was composed of methylacetate-propanol-chloro-form-methanol-0.2% (w/v) potassium chloride (25 30 20 10 10, v/v). After detection with iodine vapor (Figure 9.2), each phospholipid class was scraped off and extracted with 5 ml of methanol. The solvent was removed under a stream of nitrogen, and the fatty acids of each phospholipid class were analyzed (as their hydrazides) by HPLC. The aim of this study was to establish a standardized... 

II. Active carrier-mediated Flux is saturable with increasing concentration. Competitive substrates. Flux may be asymmetrical. Flux can be against an electrochemical gradient. Energy dependent—directly or indirectly coupled. Substrate specificity, competition, saturation. Flux is asymmetrical. 

It should now be evident that the experimental tensor may be expressed as the sum of an isotropic term resulting from the contact interaction, and a tensor resulting from dipolar interactions and any indirect coupling via the orbital angular momentum. This may be written in the form of an equation ... 

From a very general outlook, one can argue that the NMR studies of quadrupolar nuclei present in nanoscale semiconductors should offer a more incisive look into the chemical and electronic structure than do studies of spin-1/2 nuclei. The rationale is that quadrupolar nuclei can report on the same chemical, hyperftne, or Knight shifts and dipolar or indirect couplings as observed for spin-1/2 nuclei, but also provide an additional dimension of information in terms of the NQCC and associated EFGs. Although not yet reported, DFT calculations of both chemical shifts and NQCC values for the same nuclei in nano-semiconductors should provide a more stringent comparison of theoretical and experimental results, particularly if the two parameters can be correlated experimentally, as seems feasible. 

The second situation corresponds to an indirect coupling of the APC states with the ASC ones via the quantum states of the interconversion states (if). The largest contribution comes again from those state being quasi degenerate in the energy scale. Thus, to second order in TDPT one gets... 

They trigger the indirectly coupled, spontaneous relaxations 8N(AQX) and 8Q/AN), which also act toward diminishing the directly coupled forces A/jb(AN) > 0 and AFX(AQX) > 0, in accordance with the LeChatelier-Braun principle (Callen, 1962) ... 

The main NMR interactions in solution of interest to chemists are the chemical shift relative to some stated standard (6), the indirect coupling constant (7) and the relaxation times T1 (spin-lattice) T2 (spin-spin related to the line width) and T p, the relaxation time in the rotating frame. In the case of solids and oriented samples both the direct dipole-dipole and the electric quadrupole interactions assume greater importance. We shall confine our attention in this chapter to diamagnetic compounds so that we may neglect nuclear interactions with electron spins. 

H. Shimada, B. Moewes, and G. Burckhardt. Indirect coupling to Na+ of p-aminohippuric acid uptake into rat renal basolateral membrane vesicles. Am J Physiol 253 F795-F801 (1987). 

While the terminology scalar relaxation of the first kind concerns J modulation (J spin spin or scalar or indirect coupling constant) by exchange phenomena, the usual example of the second kind is a spin 1/2 nucleus (7), J coupled to a fast relaxing quadrupolar nucleus (S) with relaxation times Tj and Tf (and spin number /s)- The relevant interaction is of the form... 

Problem 4.16 What kind of alkane can be made by the indirect coupling of two molecules of RX M The product is a symmetrical alkane, R—R, whose left end is a duplicate of its right end. 

The results for the tin-containing complexes (41, 42) also permit the examination of the relationship between /pt-p trans to the tin ligand and the indirect coupling constant 2J p-pt-sn- There are accurate linear relationships for two series of complexes (see Figure 13) that... 

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